AbstractHerein, we disclose the first and simple one‐pot‐two‐step process to the synthesis of 1‐difluoromethyl 1,4‐diketones, through Mn‐catalyzed radical Brook rearrangement. The methodology is also amenable to the synthesis of 1‐trifluoromethyl 1,4‐diketones. The products are efficiently converted to fluoroalkyl substituted furans, thiophenes, pyrroles and pyridazines, which are important structural motifs in natural products and pharmaceuticals.